Catalytic conversion of hydrocarbons in the presence of regeneration gases



Aug. 12, 1952 P. c. KEITH 2,606,862

CATALYTIC CONVERSION OF HYDROCARBONS IN THE PRESENCE OF REGENERATION GASES Filed Jan. 20, 1950 INVENTOR.

Farr/1 a! K Kai/L IIENT Patented Aug. 12, 1952 CATALYTIC CONVERSION OF HYDROCAR- BONS IN .THE PRESENCE OF REGENERA:

. TION GASES Percival C. Keith, Peapack, N. 3., assignor to corporation of New J er Hydrocarbon Research Inc., New York, N. Y., a sey Application J anuary 20, 1950, Serial No. 139,758

1 V This application is a continuation-in-part of the copending application, Serial N 0. 723,345, filed January 21, 1947, now issued as U. S. Patent 2,495,262. I

The present invention relates to the high-temperature treatment-of hydrocarbons wherein a bed of comminuted contact material is alternately contacted by the hydrocarbons which are to be converted and by an oxygen-containing gas to burn off the carbonaceous matterdeposited on the contactmaterial by the hydrocarbons undergoing conversion. I v In general, prior processes of the type. contemplated by this invention have been characterized by discontinuous operation inasmuch as-the hydrocarbon stream is passed in contact with the contact material until an objectionable quantity of carbonaceous matter is'deposited on the contact materiaLthe flow of the hydrocarbon stream is then discontinued, and the carbonaceous matter is removed from the contact material by bilrning with a stream of oxygen-containing gas passed in contact therewith. Furthermore, it is customary to discard the gases resultingfrom the regeneration of the contact material since the gases generated in these prior processes have little or no practical value. It follows, therefore, that the portion of the hydrocarbon feed which goes into the formation, of the carbonaceous vdeposit on the contact material is ultimately lost by combustion which yields a valueless fiue gas.

Principal objects of this invention include the provision of a simplified process for the high-temperature treatment of hydrocarbons which is substantially continuous in operation in spite of the fact that contact material employed in the process is alternately used in the treatment of the hydrocarbons and subjected to regeneration to remove carbon therefrom, and the provision of processing conditions which avoid the wasteful consumption of carbonin the production of flue gas and lead to increased yields to .valuablehydrocarbon products.

These and other objects and advantages of the invention will be apparent from the description which follows. i Y a v I To avoid verbiage, the term, catalyst, will be hereinafterused in lieuof contact material. It is, of course, known that various contact materials have difierent propensities or activities for facilitating the conversion of hydrocarbons at elevated temperatures. Nowever, all contact materials in solid particle form as employed in the present invention have in common the function of, presenting large. surface areas to the hy- 8 claims. (on. lea-62) 2 drocarbons during their passage through the treatment'or conversion zone. Accordingly, the

. term, catalyst, is herein used in its broadest sense to connote any particulate material presenting a large'surface area to hydrocarbons undergoing conversion in order to facilitate the conversion and to hold the carbon formed during the conversion. a N

In accordance with this, invention, the hydrocarbon'stream which'is tobe subjected to hightemperature treatment or conversion isfinjected at an intermediate point ina mass of particulate catalyst disposed in the form of a plurality of serially connected beds while a regenerating gas consisting essentially of oxygen and steam is injected intotheZ'cataIyst mass at a point closer to one of the two extreme ends of theseries of catalyst beds so as to regenerate the catalyst mass in the vicinity of the point .of introduction of the regenerating gas and toeffectthe concurrent flow of the resulting regeneration gases and the hydrocarbon stream from'thel' point otintroduction of the hydrocarbon streamlt'oward the other extreme end of the series ofcatalyst beds. Periodically, the hydrocarbon stream is made to flow from its point of-intr'oduction into the catalyst mass 1 concurrently with the regeneration 'gasestoward the extreme end of ,the series of catalyst beds opposite the end toward which it Was previously flowing by shifting the point of injection of the regenerating gas closer to the extreme .end toward which the hydrocarbon stream was previously flowing. Thus, for the sake of simplicity and further clarification, if the catalyst massis arranged in two serially connected beds of equalvolume, the hydrocarbon stream is introduced :at the point of juncture of the two beds, intermediate the two extreme ends of the serially connected beds while the regenerating gas is'injected into one of the two extreme ends and made to flow toward the opposite extreme end where-a mixture of the regeneration gases and the treated or converted hydrocarbon stream is withdrawn; periodically,

the hydrocarbon conversion products are achieved by this invention through the coupling of the inherent benefits arising from the conversion of hydrocarbons by the processing procedure provided by the present invention with the selection of particular processing conditions, especially the composition of the regenerating gas, and operating temperatures and pressure.

A fundamental aspect of this invention is the discovery that under selected processing conditions, the production of nonvolatile carbonaceous matter or coke is materially suppressed by the hydrogen-containing regeneration gases which become commingled with the hydrocarbon stream undergoing treatment. This advantage is increasingly more evident with increasingly heavier charging oil stocks. Thus, while a naphtha fraction may be beneficially treated by the process of this invention, it is in the conversion of heavy oils, like topped or reduced crude petroleum, that the greatest benefits are realized. It has been found that the suppression of carbon formation is achieved to a material extent when the partial pressure of the hydrogen within the hydrocarbon conversion zone is at least about '75 p. s. i. (pounds per square inch) and preferably at least about 100 p. s i. It is curious to note that maximum benefits from the presence of hydrogen generally occur at hydrogen partial pressure not exceeding about 200 p. s. i. so that thereis little or no justification in seeking a hydrogen partial pressure greater than about 200 p. s. i.

To obtain the desired hydrogen partial pressure in the hydrocarbon conversion zone, the a whole reaction system is maintained at a pressure in the range of about 200 to 800 p. s. i. g. (pounds per square inch gauge), preferably in the range bfabout 300 to 650 p. s. i. g., and the carbon deposit on the catalyst particles is removed therefrom by reaction with a regenerating gas consisting essentially of a preponderance of steam and a minor proportion of high-purity oxygen under conditions favoring the production of hydrogen in the regeneration zone. More specifically, the high-purity oxygen may be the product of air liquefaction and rectification containing at least about 90% by volume of oxygen, preferably at, least about 95% by volume of oxygen.

The principal reactions by which the carbon deposit is eliminated from the catalyst particles include:

Another important reaction taking place in the regeneration zone is the water-gas shift reaction:

Reactions A,'B and E are exothermic While reactions C and D are endothermic. Reactions D and E produce the hydrogen employed by this invention in improving the hydrocarbon conversion step. The regenerating gas contains an excess of steam or water vapor over oxygen to ensure maximum yield of hydrogen. From the viewpoint of stoichiometry, a regenerating gas comprising about 2 volumes of water vapor for each volume of oxygen would have an adequate proportion of water vapor to assure a high yield of hydrogen in the regeneration product gases.

fit

However, as a practical matter, since the temperature of the catalyst particles and the materials of construction of the reactor generally must be kept below 3000 F. to avoid fusion or other injury, it is necessary to employ a considerably largersteam-to-oxygen ratio, at least of the orderof 3:1. Refractory materials like zirconia from which the catalyst particles and reactor lining can be made to withstand elevated temperaturesranging up to about 3000 F. are fairly expensive and, therefore, it is frequently advisable to choose from the cheaper refractories which usually can withstand temperatures not exceeding about 2500 F. Steam-to-oxygen ratios in the range of about 3:1 to 7:1 are generally satisfactory for maintaining the regeneration temperature in the desirable range of about 1600 to 2500 F. For the purposes of this invention which depends upon an appreciable production of hydrogen during the regeneration of the catalyst, the regeneration temperature must not be permitted to-fall below about 1400 F. In short, it is advisable to conduct the regeneration at temperatures approaching the maximum temperature permissible with the chosen catalyst particles and reactor materials, and this means in turn, that the regenerating gas should have the smallest steam'-tooxygen ratio which will afford the necessary temperature control. In most instances, regeneration is carried out at temperatures in the range of substantially 1600 to 2500 F. with regenerating gases having steamto-oxygen ratios in the range of substantially 3:1 to 7:1." 1 V The beneficial influence of the regeneration product gases which contain a material proportion of hydrogen and which become commingled withfthe' hydrocarbon stream in the conversion zone is principally attained when the conversion zone is maintained at temperatures in the range of about 800 to 1050" F. Optimum conversion results are generally obtained at temperatures in the range of about 850 to 950 F. 7

To attain desired reforming or conversion of heavy oil molecules, it is necessary to maintain a substantial partial pressure of oil, usually about 40 to p. s. i. in the conversion zone. Such a substantial oil partial pressure is ensured by operating the reaction system at an elevated pressure in the range of about 200 to 800 p. s. i. g.

It is highly advisable to preheat all of the reactants entering the reaction system to the highest practical temperatures approaching the respectivereaction temperatures of these reactants. For instance, since the regeneration zone is operated at temperatures of not less than about 1400" F., the regenerating gas is usually charged at temperatures in the vicinity of 1000 F.; specifically, steam may be supplied at a temperature of about 900 to 1100 F. along with highpurity oxygen preheated to a temperature of about 400 to 800 F. With the conversion zone operating at temperatures of not less than about 800 F., it is desirable to preheat the hydrocarbon stream to a temperature as close to the conversion temperature as is possible Without causing coking or other hydrocarbon degradation in the preheater. Most hydrocarbon feed stocks can be safely preheated to temperatures in the range of 600 to 750 F.

Suitable contact materials or catalysts include quartz chips, alumina, magnesia, zircon, beryl and bauxite. It is clear that the catalyst should be selected on the. basis of its ability to withstand the desired regeneration conditions includin place in reactor I5 by a lower foraminous member or perforated plate It and an upper foraminous member or perforated plate I5. To facilitate the introduction of the reactants, the serially disposed catalyst beds I3 are preferably spaced so as to leave a distributing zone it between each pair of contiguous beds I3.

The hydrocarbon feed stock is supplied by line I? to a preheating furnace i8 whence it is conveyed by line I9 to the middle of elongated reactor I G. The charged hydrocarbon stream flows through reactor Ii! from the mid-point of introduction either upwardly to extremity I i or downwardly to extremity I2 depending upon whether the regenerating gas is introduced into the lower extremity I2 or into the upper extremity II, respectively.

The regenerating gas consisting essentially of a preponderance of steam and a minor proportion of high-purity oxygen is supplied by line 28 having an upper branch line 2I extending to line 22connected to upper extremity Ii and a lower branch line 23 extending to line 25 connected to lower extremity I 2. Upper branch line H is provided with a valve 25 whilelower branch line 2-3 is provided with a valve 26. During one period or cycle of operation the regenerating gas is made to flow into lower extremity I2 of reactor H by closing valve 25 and opening valve 26. Under these conditions, carbonaceous matter deposited in the catalyst beds M of the lower half of reactor !8 during the preceding period or cycle of operation is eliminated from these beds by reacand regeneration product gases containing hydrogen continue to flow upwardly through the catalyst beds I3 of the upper half of reactor If! under conditions promoting the desired conversion of the hydrocarbon stream. The treated or converted hydrocarbon stream admixed with the regeneration gases leaves extremity II of reactor II! by way of line 22 which discharges into line 21 which, in turn, conveys the total reaction effluent to a suitable separation plant wherein this reaction efiluent is separated into desired product fractions. I will be appreciated that in addition to liquid hydrocarbon fractions like gasoline, there is recovered from the total reaction efiiuent a normally gaseous fraction which is valuable in view of its high heating value and its suitability for use in other chemical reactions, particularly the catalytic synthesis of hydrocarbons and oxygenated hydrocarbons from hydrogen and carbon monoxide. Line 22 is provided with a valve 28 which is opened when the reaction effluent is passing from upper extremity iI of reactor it through line 22; at the same time, valve 29 in line 24 is kept closed.

In the next period or cycle of operation the regenerating gas is made to flow through upper 6 branch line 2| by'closing valve 26 and opening valve 25. Similarly, valve 28 is closed and valve 29 is opened. Under thesecircum'stances, theregenerating gas enters upper extremity II-and flows downwardly through catalyst beds-I3 in the upper half of reactor I0 to effect the removal of carbonaceous matter laid downtherein during the preceding cycle of operation by the hydrocarbon stream undergoing conversion; the regeneration product gases become commingled with the hydrocarbon stream entering the midpoint of reactor Ill and continue toflow downwardly under hydrocarbon conversion conditions through catalyst beds I3 in the lower half of re-: actor ID. The total reaction eflluent'leaves lower extremity I2 by way of line 24 connected-to line 27 which conveys the reaction efiiuent to the separation 'plant. When this cycle of operation reaches the point where it becomes necessary to regenerate catalyst beds I3 in 'thelower half of reactor Iii, the first-described cycle is repeated by closing valves and 291and-opening'valves 26 and 28. Again, when the catalyst beds It, of the upper half of reactor Ill require regeneration, the introduction of regenerating gas is shifted from the lower extremity I2 .to' upper extremity I I by opening valves 25 and 23 and closing valves 25and28. M

It is clear from the foregoing description that through the simple alternation ofthe point of introduction of the regenerating g-asgthe hydrocarbon stream changes itsdirection of flow from spent or fouled catalyst bedsto regenerated catalyst beds without necessitating any interruption in the charging of they hydrocarbon stream to reactor Id. In other words, the hydrocarbon feed I stock passing through line H, preheater I 8 and line I9 may flow continuously at a desired, uniform rate without regard .to its changing direction of flow through reactor I6 as necessitated by the periodic regeneration of the several catalystbeds I3. I i

With the heavier hydrocarbon feed stocks, a

sufiicient quantity of carbonaceous matter will be laid down on the catalystduring the conversion cycle to ensure an adequate production of hydrogen during the regeneration cycle so that the commingled regeneration product gases and the hydrocarbon feed stream will have a hydrogen partial pressure of at least about 7-5 p. s. i. and preferably at least about p. s. i. However, when such a hydrogen partial pressure cannot be obtained because of a deficiency of carbon laid down on the catalyst by the hydrocarbon feed during conversion, the desired hydrogen partial pressure can be attained by supplementing the hydrogen formed during regeneration in the reactor with hydrogen separated fromthe total reaction efliuent and recycled to the, reactor. In such case, there is separated from the total reaction efiiuent a gaseous fraction which is rich in hydrogen and this fraction is recycled to the reactor. As shown in the drawing, the hydrogencontaining fraction maybe recycled by line 35 a, which is connected with hydrocarbon feed line I1. If desired, a portion or all of the recycled gas may be diverted throughline 3 I connected to line I9. Similarly, for flexibility and control of process condition-s, a portion of the hydrocarbon stream may by-pass preheater I3 byway of line 7 into each of the distributing zones It in the upper half of reactor when the catalyst is being regenerated in this portion of reactor and, likewise, branch line 23 may be provided with valved branches 34 to supply the regenerating gas individually to the catalyst beds [3' in the lower half of reactor l0 during the next cycle of operation. When the regenerating gas is being charged into the upper portion of reactor [0, the gas maybe evenly divided for simultaneous passage through open valves 25 and 33. Alternatively, most or all of the gas may at first pass through valve 25 and gradually the gas flow maybe shifted to the uppermost valve 33, then to the next lower valve 33, and so on; in the next cycle of operation, most or all of the gas at first flows through valve 23 and gradually the gas flow is shifted to the lowermost valve 34, then to the next higher valve 34, and so on. Similarly, line [9 may have upper valved branches 35 and lower valved branches 36. Thus, it is possible to divide the hydrocarbon feed stream evenly for injection into each of the catalyst beds l3 in the upper half of reactor l0 during one cycle of operation and into each of the catalyst beds 13 in the lower half of reactor I 0 during the next cycle of operation. Also, the hydrocarbon stream may at first flow directly from line iii to the middle of reactor 10 and, in the course of the cycle when regeneration is being carried out in the lower half of reactor ID, the hydrocarbon flow may be shifted to the lowermost branch 35, then to the next higher branch 35, and so on. In the succeeding cycle when regeneration is carried out in the upper half of reactor 20, the hydrocarbon flow is shifted from the uppermost branch 35 back to the middle of reactor l0 and, during this cycle, the hydrocarbon flow is gradually shifted to the uppermost branch 36, then to the next lower branch 36, and so on. When the next cycle of regeneration in the lower half of reactor I0 is initiat'ed, the flow of hydrocarbon is' transferred from the lowermost branch 36 back to the middle of reactor (0 by direct injection through line [0 and the flow sequence just described is repeated.

Through still another simple modification, it is possible to strip with steam adsorbed hydrocarbons from fouled catalyst before it is sub-- jected to regeneration and, likewise, to strip with steam adsorbed oxygen from regenerated catalyst before hydrocarbons are brought into contact therewith. As shown in the drawing, the supply end of line '20 has a branch A through which steam is fed and a branch 203 provided with valve 200 for supplying high-purity oxygen. Thus, when it is desired to strip the catalyst with steam between each alternation from a conversion cycle to a regeneration cycle and vice versa, the supply of oxygen may be momentarily interrupted by closing valve 20C. For instance, assuming that the switching from the conversion cycle to the regeneration cycle is made every 16 minutes, valve 200 may be closed for the first minute of the 16-minute period so that steam alone passes through the portion of the catalyst to be regenerated in order to purge or strip hydrocarbon-s therefrom, valve 200 may then be opened for 14 minutes to effect oxidative regeneration of the catalyst, and for the last minute of the 16- minute period valve 20C may again be closed so that the continuing flow of steam urges the regenerated catalyst of residual oxygen just before the hydrocarbon stream is made to flow in contact with the regenerated catalyst in the succeeding 16-minute period. v

It is seen from the foregoing illustrative modifications that through the simple manipulation of valves various flow sequences of the reactants entering the reactor can be achieved to afford greater flexibility and control of the process conditions.

As a specific example of the invention, East Texas Black oil having 14 API gravity is treated in a reactor as shown in the drawing containing beds of approximately /g-iIlCh diameter pellets prepared from alumina gel. With an oil charging rate of 10,000 barrels per day, oxygen of by volume purity is supplied at the rate of 4.23 millions of cubic feet (standard conditions) per day together with 950,000 lbs. per day of steam as the regenerating gas (steam-tooxygen ratio of 5:1). The oil is preheated to a temperature of 700 the oxygen to 450 F. and the steam to 1000 F. The total depth of contact pellets in the reactor is about 30 feet and the reactor is 15 feet in diameter. A gauge pressure of 600 p. s. i. is maintained in the reactor, the hydrogen partial pressure being 180 p. s. i. The average temperatures in the regeneration and conversion zones are about 1900" F. and M0 R, respectively. The switching between conversion and regeneration zones is made every 25 minutes. From the total reaction effluent, there are recovered each day the following liquid products:

The rest of the charged oil is recovered in the form of fuel gas (approximately 25 millions of standard cubic feet per day) having a heatin value of about 430 B. t. u. per standard cubic foot. The gasoline thus produced has an ASTM motor octane number of 78.

In view of the various modifications of the invention which will occur to those skilled in the art upon consideration of the foregoing disclosure without departing from the spirit or scope thereof, only such limitations should be imposed as are indicated by the appended claims.

What I claim is:

1. The process of treating hydrocarbons by passage through a mass of catalyst wherein carbonaceous matter is deposited by said hydrocarbons during passage therethrough and periodically said carbonaceous matter is removed by a regenerating gas, which comprises maintaining said mass at a pressure of about 300 to 650 p. s. i. g., supplying to said mass in the vicinity of one end thereof a regenerating gas consisting essentially of steam and oxygen of at least about 95% by volume purity in the respective molar proportions of about 3:1 to '7 :1 to effect removal of said carbonaceous matter by conversion at a temperature of about 1600 to 2500 F. to a regeneration product gas consisting predominantly of hydrogen and carbon monoxide, flowing said product gas through said mass toward the opposite end thereof and simultaneously injecting said hydrocarbons into said product gas at a point in said mass intermediate said ends, maintaining a temperature of about 850 to 950 F. and

a hydrogen partial pre ssureofabout100 to 200 p. at in the resulting mixture of said product gas and said hydrocarbons, withdrawing said mixture from said massin the vicinityof said opposite end, and periodically reversing the flow ofsaid mixture through said mass by. supplying saidregenerating gasin the vicinity of said opposite end and withdrawing said mixture in the vicinity of the first said end.

2. 'Ihe process of converting heavy hydrocarbons of the type oftopped petroleum crude oil principally to high-quality gasoline bypassage of said hydrocarbons through a mass of catalyst wherein carbonaceousmatter is deposited by said hydrocarbons during passage therethro-ughand periodically said carbonaceous matteris removed by a regenerating gas, which comprisesmaintaining said mass at a pressure of about 200 to 800 p. s. i. g., supplying to said mass in the vicinity of one end thereof a-regenerating gas con-'- sisting essentially of steam and oxygen of at least about 90% by volume purity in the respective molar proportions of about 3:1 to 7:1 to effect removal of said carbonaceous matter by conversion at a temperature of about 1600 to 25 00 F. to a regeneration product gas consisting predominantly of hydrogen and-carbon monoxide, flowing said product gas through said mass toward the opposite end thereof and simultaneously injecting said hydrocarbons into said product gas at a point in said mass intermediatesaid ends, maintaining a temperature of about8 50 to 950 F. and a hydrogen partial pressure of about 100 to 200 p. s. i. in the resultingmixture of said product gas and said hydrocarbons, withdrawing said mixture from said mass in the vicinity of said opposite end, recovering from the withdrawn mixture high-quality gasoline as the principal product of conversion of said hydrocarbons, and

periodically reversing the flow of said mixture through said mass by supplying said regenerating gas in the vicinity of said opposite end and withdrawing said mixture in the .vicinity of the first said end.

3. The process. .of converting hydrocarbonsby passage through a mass of catalyst wherein carbonaceous matter is deposited by said hydrocarbons during passage therethrough and periodically said carbonaceous matter is removed by a regenerating gas, which comprises-maintaining said mass at a pressure of about 200 to 800 p. s. i. g. in fluid-communicating conversion and regeneration zones, supplying to said regeneration zone regenerating gas consisting essentially of steam and oxygen of at least about 90% by volume purity in the respective molar proportions of about 3:1 to 7:1 to efiect removal of said carbonaceous matter by conversion at a temperature of about 1600 to 2500 F. to a regeneration product gas consisting predominantly of hydrogen and carbon monoxide, flowing said product gas through said conversion zone and simultaneously injecting said hydrocarbons into said product gas, maintaining a temperature of about 800 to 1050 F. and a hydrogen partial pressure of about 100 to 200 p. s. i. in the resulting mixture of said product gas and said hydrocarbons in said conversion zone, withdrawing said mixture from said conversion zone, and periodically switching said conversion and regeneration zones by supplying said regenerating gas to the aforesaid conversion zone and withdrawing said mixture from the aforesaid regeneration zone.

4. The process of converting hydrocarbons by passage through a mass of catalyst wherein carbonaceous matter is deposited-by said hydrocarbons during passage therethroughand said carbonaceous matter is subsequently removed by a regenerating gas, which comprises maintaining said mass at a pressure of about 200 to 800 p-. s. i. g. in fluid-communicating conversion and regeneration zones, supplying to said mass in said regeneration zonea regenerating gas consisting essentially of steam and oxygen, of atleast about by volume purity in the respective molar proportions of about 3:1 to 7:1 to efiect removal of said carbonaceous matter by conversion at a temperature of about 1600?; to 2500 F. to aregeneration product gas consisting predominantly of hydrogen and carbon monoxide, flowingsaid product gas through said massin said; conversion zone and. simultaneously and continuously injecting said hydrocarbons into said product gas while said product gas is flowing through said conversion zone, maintaining a temperature of about 800 to 1050 F. and a hydrogen partial pressure. of 75 to 200 p. s. i. in the resulting mixture of said product gas and said hydrocarbons, withdrawing said mixture, from said conversion zone, and subsequently subjecting said mass in said conversion zone to the action of said regenerating gas and said mass in said regeneration zone to the action of said mixtureof regeneration product gas and hydrocarbons. V

5. The process of converting heavy hydrocarbons of the type of topped petroleum crude oil by passage through a;mass of catalyst wherein carbonaceous matter is deposited by said hydrocarbons during passage therethrough and said carbonaceous matter is subsequently removed by a regenerating gas, which.comprises maintaining said mass at a pressure of about 3.00 to 650 p. s. i. g. in fluid-communicating conversion and regeneration zones, supplying to said mass in said regeneration zone a regenerating gasconsisting essentially of steam and oxygenof at least about 90% by volume purity in the respective molar-proportions of about 3:1 to 7:1 to effect removal of said carbonaceous matter by conversion at a temperature of about 1600 to 2500F. to a regeneration product gas consisting predominantly of hydrogen and carbon monoxide, flowing said product gas through said mass in said conversion zone and simultaneously and'continuously injecting said hydrocarbons into? said product'gas while said product gas is flowing through'said conversion zone, maintaining a temperature of about 800 to 1050 F. and a hydrogen partial pressure of about to 200 p. s. i. in the resulting mixture of said product gas and said hydrocarbons, withdrawing said mixture from said conversion zone, and subsequently subjecting said mass in said conversion zone to the action of said regenerating gas and said mass in said regeneration zone to the action of said mixture of regeneration product gas and hydrocarbons.

6. The process of converting hydrocarbons by passage through a mass of catalyst wherein carbonaceous matter is deposited by said hydrocarbons during passage therethrough and said carbonaceous matter is subsequently removed by a regenerating gas, which comprises maintaining said mass at a pressure of about 200 to 800 p. s. i. g. in fluid-communicating conversion and regeneration zones, supplying to said mass in said regeneration zone a regenerating gas consisting essentially of steam and oxygen of at least about 90% by volume purity in the respective molar proportions of about 3:1 to 7:1 to effect removal of said carbonaceous matter by conversion 11 at a temperature of about 1600- to 2500 F. to a regeneration product gas consisting predominantly of hydrogen and carbon monoxide, flowing said product gas through said mass in said conversion zone and simultaneously and continuously injecting said hydrocarbons into said product gaswhile said product gas is flowing through said conversion zone, maintaining a temperature of about 850 to 950 F. and a hydrogen partial pressure of 75 to 200 p. s. i. in the resulting mixture of said product gas and said hydrocarbons, Withdrawing said mixture from said conversion zone, and subsequently subjecting said mass which has been exposed to said mixture of said product gas and saidhydrocarbons to contact with said regenerating gas and subjecting said mass which has been exposed to said regenerating gas to contact with said mixture of said product gas and said hydrocarbons.

7. The process of converting hydrocarbons by passage through a mass of catalyst wherein carbonaceous matter is deposited by said hydrocarbons during passage therethrough and said carbonaceous matter is subsequently removed by a regenerating gas, which comprises maintaining said mass at a pressure of about 300 to 650 p. s. i. g. in fluid-communicating conversion and regeneration zones, supplying to said mass in said regeneration zone a regenerating gas consisting essentially of steam and oxygen of at least about 90% by volume purity in the respective molar proportions of about3zl to 7:1 to efiect removal of said carbonaceous matter by conversion at a temperature of about 1600 to 2500 F. to a regeneration product gas consisting predominantly of hydrogen and carbon monoxide, flowing said product gas through said mass in said conversion zone and simultaneously and continuously injecting said hydrocarbons into said product gas while said product gas is flowingthrough said conversion zone, maintaining a temperature of about 800 to 1050 F. and a hydrogen partial pressure of about 75 to 200 p. s. i. in the resulting mixture of said product gas and said hydrocarbons, withdrawing said mixture from said conversion zone, and subsequently subjecting said mass which has been exposed to said mixture of said product gas and said hydrocarbons to contact with said regenerating gas and subjecting said mass which has been exposed to said regenerating gas to contact with said mixture of said product gas and said hydrocarbons.

"8. The process of 'convertingheavy hydrocarbons of the type of topped petroleum crude oil by passagethrough a mass of catalyst wherein carbonaceous matter is deposited by said hydrocarbons'during passage therethrough and said carbonaceous matter is subsequently removed by a regenerating gas, which comprises maintaining said mass at a pressure of about 200 to 800 p. s. i. g. in fluid-communicating conversion and regeneration zones, supplying to said mass in said regeneration zone a regenerating gas consisting essentially of steam and oxygen of at least about by volume purity in the respective molar proportions of about 3:1 to 7:1 to effect removal of said carbonaceous matter by conversion at a temperature of about 1600 to 2500 F. to a regeneration product gas'consisting predominantly of hydrogen and carbon monoxide, flowing said product gas through said mass in said conversion zone and simultaneously and continuously injecting said hydrocarbons into said product gas while said product gas is flowing through said conversion zone, maintaining a temperature of about 800 to 1050 F. and a hydrogen partial pressure of about '75 to 200 p. s. i. in the resulting mixture of said product gas and said hydrocarbons, withdrawing said mixture from said conversion zone, and subsequently subjecting said mass which has been exposed to said mixture of said product gas and said hydrocarbons to contact with said regenerating gas and subjecting said mass which has been exposed to said regenerating gas to contact with said mixture of said product gas and said hydrocarbons.

PERCIVAL C. IGIITH.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,450,753 Guyer Oct. 5, 1948 2,495,262 Keith Jan. 24, 1950 OTHER REFERENCES Fuels and Their Combustion by Haslam and Russell, McGraw Hill Book Co., New York, 1926, pages 162 and 163. 

1. THE PROCESS OF TREATING HYDROCARBONS BY PASSAGE THROUGH A MASS OF CATALYST WHEREIN CARBONACEOUS MATTER IS DEPOSITED BY SAID HYDROCARBONS DURING PASSAGE THERETHROUGH AND PERIODICALLY SAID CARBONACEOUS MATTER IS REMOVED BY A REGENERATING GAS, WHICH COMPRISES MAINTAINING SAID MASS AT A PRESSURE OF ABOUT 300 TO 650 P.S.I.G., SUPPLYING TO SAID MASS IN THE VICINITY OF ONE END THEREOF A REGENERATING GAS CONSISTING ESSENTIALLY OF STEAM AND OXYGEN OF AT LEAST ABOUT 95% BY VOLUME PURITY IN THE RESPECTIVE MOLAR PROPORTIONS OF ABOUT 3:1 TO 7:1 TO EFFECT REMOVAL OF SAID CARBONCAEOUS MATTER BY CONVERSION AT A TEMPERATURE OF ABOUT 1600* TO 2500* F. TO A REGENERATION PRODUCT GAS CONSISTINGD PREDOMINANTLY OF HYDROGEN AND CARBON MONOXIDE, FLOWING SAID PRODUCT GAS THROUGH SAID MASS TOWARD THE OPPOSITE END THEREOF AND SIMULTANEOUSLY INJECTING SAID HYDROCARBONS INTO SAID PRODUCT GAS AT A POINT IN SAID MASS INTERMEDIATE SAID ENDS, MAINTAINING A TEMPERATURE OF ABOUT 350* TO 950* F. AND A HYDROGEN PARTIAL PRESSURE OF ABOUT 100 TO 200 P.S.I. IN THE RESULTING MIXTURE OF SAID PRODUCT GAS AND SAID HYDROCARBONS, WITHDRAWING SAID MIXTURE FROM SAID MASS IN THE VICINITY OF SAID OPPOSITE END, AND PERIODICALLY REVERSING THE FLOW OF SAID MIXTURE THROUGH SAID MASS BY SUPPLYING SAID REGENERATING GAS IN THE VICINITY OF SAID OPPOSITE END AND WITHDRAWING SAID MIXTURE IN THE VICINITY OF THE FIRST SAID END. 